Solid-state electrochemical kinetics of Li-ion intercalation into Li1-xCoO2: simultaneous application of electroanalytical techniques SSCV, PITT, and EIS

M. D. Levi, G. Salitra, B. Markovsky, H. Teller, D. Aurbach, Udo Heider, Lilia Heider

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608 Scopus citations

Abstract

The electroanalytical behavior of thin Li1-xCoO2 electrodes is elucidated by the simultaneous application of three electroanalytical techniques: slow-scan-rate cyclic voltammetry (SSCV), potentiostatic intermittent titration technique, and electrochemical impedance spectroscopy. The data were treated within the framework of a simple model expressed by a Frumkin-type sorption isotherm. The experimental SSCV curves were well described by an equation combining such an isotherm with the Butler-Volmer equation for slow interfacial Li-ion transfer. The apparent attraction constant was -4.2, which is characteristic of a quasi-equilibrium, first-order phase transition. Impedance spectra reflected a process with the following steps: Li+ ion migration in solution, Li+ ion migration through surface films, strongly potential-dependent charge-transfer resistance, solid-state Li+ diffusion, and accumulation of the intercalants into the host materials. An excellent fit was found between these spectra and an equivalent circuit, including a Voigt-type analog (Li+ migration through multilayer surface films and charge transfer) in series with a finite-length Warburg-type element (Li+ solid-state diffusion), and a capacitor (Li accumulation). In this paper, we compare the solid-state diffusion time constants and the differential intercalation capacities obtained by the three electroanalytical techniques.

Original languageEnglish
Pages (from-to)1279-1289
Number of pages11
JournalJournal of the Electrochemical Society
Volume146
Issue number4
DOIs
StatePublished - Apr 1999

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